Synthesis, Structural Characterization, and Reactivity of (8-Methoxynaphthyl)hydridogermanium Triflates and Iodides

New 8-(methoxynaphthyl)hydridogermanium triflates and iodides were synthesized by treatment of the corresponding germanes with trifluoromethanesulfonic acid or I₂. Their characterization by ¹H and ¹³C NMR and IR spectroscopy is reported. In the solid state, bis(8-methoxynaphthyl)hydridogermanium triflate (6) exhibits a 5-coordinate germanium atom weakly linked to the triflate anion. The germyl iodide rapidly gives the germoxolene with loss of MeI when it is heated in CH₃CN. With H₂O, amine, and DMSO, the germyl triflates react quantitatively to form new complexes which can be isolated and characterized. The X-ray crystal structure of the hydrate of bis(8-methoxynaphthyl)hydridogermanium triflate (11) shows the predominant formation of a hydrated germyl cation. Several tentative approaches to prepare germanols failed and always gave stable germoxanes instead.